Non-caking alkyl aryl sulfonate



Unite rates 'atent 2,717,243 Sept. 36, 1955 NON-CAKIN G ALKYL ARYLSULFONATE DETERGENT COMPOSITIONS Herman S. Bloch, Chicago, and George L.Hervert,

Downers Grove, Ill., assignors to Universal Oil Products Company,Chicago, 111., a corporation of Delaware No Drawing. Application June19, 1951, Serial No. 232,478

18 Claims. (Cl. 252138) This invention relates to a detergentcomposition in comminuted form containing a combination of ingredientsincluding an active, water soluble, but normally hygroscopic detergentsalt which in the presence of the remaining ingredients of the presentcomposition may exhibit substantially no tendency to cake upon storageat relatively high temperatures or high atmospheric humidity. Morespecifically, the present invention concerns a detergent compositioncontaining a relatively high melting point, anti-hygroscopic componentin combination with an ingredient which enhances the solubility of theremaining components in aqueous solution.

The hygroscopicity of certain anionic detergents in contact with humidatmospheres which may, even at rela tive low humidities, cause thedetergent to deliquesce and to subsequently cake and the low meltingpoint of other detergents which causes a detergent compositioncontaining the same to agglomerate into larger aggregations of particleshave been common and widely recognized problems in the manufacture andsale of compositions containing such detergents. The problem isparticularly manifest in packaging of commercial detergent compositionswhere the deliquescent property of the detergent and/or its low meltingpoint results in the tendency of the product to clog in the packagingmachines or to form a rigid cake or a mass of hard lumps in the package,the composition losing the original free-flowing characteristics of thesmall particles and in its lump form requiring a longer period todissolve in water when utilized by the consumer. This tendency of thecomminuted detergent composition to absorb moisture from the surroundingatmosphere or to fuse into larger agglomerates when the atmospherictemperature increases and subsequently form the undesirable aggregatesof the particles thus negatives the intended effect of originallyforming the composition in comminuted form to enhance the free-flowingcharacteristics and rapid solubility of the product in water.

One of the primary objects of this invention is to provide a comminuteddetergent composition containing a highly efiective, but normallyhygroscopic detergent salt,

and a component which reduces the tendency of the anionic detergentcomponent to agglomerate into lumps or into a hard, relatively solidaggregation of detergent particles. Another object of the presentinvention is to provide a detergent composition which remains infreeflowing, readily water-soluble condition during storage at hightemperatures or in atmospheres of relatively high humidity. Stillanother object of the invention isv to provide a process for intimatelyadmixing an anti-hygroscopic agent with a normally hygroscopic anionicdetergent and incorporating therein a component which promotes thewater-solubility of the anti-hygroscopic agent.

In one of its embodiments, the present invention relates to a comminuteddetergent composition comprising: (1) a detergent selected from thegroup consisting of a normally hygroscopic and the relatively lowmelting point alkyl aromatic sulfonate salts, (2) an alkyl aromaticsulfonate salt of a metal selected from theelements of groups 2 II andIII of the periodic table, and (3) a sequestering agent for said groupIf and group III metal sulfonate salts.

A more specific embodiment of the invention concerns a detergentcomposition comprising: (1) a detergent salt selected from the groupconsisting of an alkali metal, an ammonium, an alkyl ammonium, and ahydroXy-alkyl ammonium salt of an alkyl benzenoid sulfonic acid, (2)from about 5 to about 50% by Weight of said composition of the magnesiumsalt of an alkyl benzenoid sulfonic acid, and (3) an alkali metalpolyphosphate sequestering agent for said magnesium salt, said alkylbenzenoid sulfonic acid containing an alkyl substituent having fromabout 9 to about 18 carbon atoms per alkyl substituent.

Other objects and embodiments of the present invention relating tospecific components of the detergent composition, to special methods ofincorporating the antihygroscopic agent into the composition, and otherfactors involved in the production of the present product will bereferred to in greater detail in the following further description ofthe invention.

The component of the present detergent composition broadly referred toherein as an anionic alkyl benzenoid sulfonate salt is a Water-solubledetergent compound which under normal conditions, in the absence of anaccompany ing anti-hygroscopic agent, tends to undergo deliquescencewhen in contact with a humid atmosphere in storage or under otherconditions normally obtaining during the manufacture or use of detergentproducts. The anionic detergent component is further characterized inbeing a member of the class of compounds which are ionically stable inaqueous solution and in the presence of alkaline earth metal ions andother heavy metal ions generally present in the so-called hard waterscommonly used in domestic and industrial deterging operations.Detergents having these characteristics are usually selected from thesulfate, sulfonate and phosphonate salts prepared from syntheticallyproduced organic charging stocks. It is thus intended to exclude suchdetergents as the sodium and potassium salts of long chain fatty acidsknown as soaps which form a water-insoluble curd when dissolved in Watercontaining magnesium or calcium ions in solution. Al though many anionicdetergents are characterized by deliquescence and/ or low meltingpoints, the group repre! sented by the commonly used anionic syntheticwetting agents and detergents are particularly adapted for use in thepresent detergent composition, including, for example, the alkylsulfonate class of compounds, such as sodium cetylsulfonate, sodiumlauryl sulfonate, etc.; the alkanol sulfate type, such as themono-sodium salt of the sulfate esters of lauryl and cetyl alcohols; thealkylaryl sulfonates of both the monoand polynuclear aromatichydrocarbons and their homologs, as for example, the alkali metal saltsof decyl-, dodecyl-, pentadecyl-, hexadecyb, and octadecylbenzenesulfonic acids, the corresponding alkyl substituted sodium toluenesulfonate salts, sodium alkyl tetralinsulfonates, and sodiumisopropylnaphthalene sulfonate, etc.; the alkali metal salts of thesulfated fatty acid monoglycerides, such as a sodium or potassium saltof the mono-glyceride esters of oleic, stearic, palmitic, and margaricacid sulfates; the alkylated phenol sulfonates, such as the sodiumsulfonate salt of butylphenylphenol; the alkali metal succinate andsulfosuccinate salts, such as the alkali metal salts ofdioctylsulfosuccinic acid ester; the alkyl and alkyl aromaticphosphonate salts, such as sodium lauryl phosphonate, sodiumdodecylbenzene phosphonate, etc., and other anionic detergents whichhave relatively low melting points or which generally deliquesce inhumid atmospheres. Although the potassium and sodium salts of thevarious organic acid radicals involved in the structure of suchdetergents are most widely used, the salts of ammonia, alkyl amines(Which form the corresponding alkyl ammonium salts when the amine isreacted with the organic acid radical) and the alkanol amines andpolyalkanol amines (which form the corresponding hydroxyalkyl ammoniumsalts of the organic acid radical) may likewise be utilized in thepresent composition and in the case of certain preparations, such asshampoos, etc., the latter ammonium salt derivatives may be preferred.

An anionic detergent which is presently being widely used in commercialand domestic applications, particularly adaptable for use as thedetergent component of the present composition, is the type known asalkyl aromatic sulfonate salts, and particularly the sodium sulfonatesalts which tend to cake rapidly upon storage in bulk at highatmospheric temperatures and humidities. The most effective detergentsof the alkyl aromatic sulfonate class are preferably benzenoid instructure, containing an alkyl group having from about 9 to about 18carbon atoms per group, although the alkyl polycyclic aromatic sulfonatetypes containing alkyl groups having up to about 9 carbon atoms peralkyl group, such as the nonylnaphthalene sulfonate salts, theamylmethylnaphthalene sulfonate salts, etc., comprise useful detergentingredients which may be incorporated into the present detergentcomposition. The long chain alkyl benzene sulfonate salts, such assodium dodecylbenzene sulfonate generally tend to cake less readily thanthe corresponding monolong chain alkyl substituted toluene sulfonatesbecause of their higher melting points and their lesser tendency todeliquesce in the presence of humid atmospheres. However, even thoughrelatively more resistant to caking than the corresponding toluenederivative salts, the long chain alkyl benzene sulfonates exhibit markedtendencies to cake when composited with other common detergentcomposition ingredients such as builder salts, extenders, etc.,hereinafter more specifically characterized, as compared with soaps orother anionic detergents such as, for example, sodium lauryl sulfate.Furthermore, the structure of the long chain alkyl group attached to thearomatic nucleus of the detergent molecule may have marked influenceupon the hygroscopicity and melting point of the detergent. Thus, whenthe long chain alkyl substituent attached to the aromatic nucleus is ahighly branched chain alkyl group, such as a polypropylene alkyl group,the sulfonated and neutralized product forms an especially effectivedetergent product, which is likely to be more deliquescent and have alower melting point than the corresponding detergent prepared from amore relatively straight chain alkyl group on the benzenoid hydrocarbonnucleus. It is thus evident that the tendency of a given detergentcomposition to undergo caking at relatively high atmospheric temperatureand/or humidity is dependent upon a large number of factors.

The effectiveness of the detergent component in its detersive action inan aqueous solution thereof is enhanced by compositing the same with aso-called builder salt or a mixture of several of such salts, which inthemselves may be deliquescent and which generally lower the meltingpoint of the detergent component, especially when composited in intimateadmixture therewith. Suitable builder salts for this purpose may beselected from the group comprising one or a mixture of the water-solublealkali metal, ammonium, amine, or alkanol amine sulfates, chlorides,phosphates, dihydrogen phosphates, silicates, borates, carbonates, andpolyphosphates, the preferred members of this group consisting of thealkali metal sulfates, phosphates and polyphosphates. Of the latter,sodium sulfate and the sodium polyphosphates, as for example,tctrasodiump'yrophosphate or sodiumtripolyphosphate are preferred whencomposited with an alkyl aromatic sulfonate salt. The builder salt, whenincorporated in the present detergent composition, is added thereto inamounts ranging from about 10 to about 85% by weight thereof, preferablyfrom about to about 65% by weight of the final detergent composition.Although the presence of the builder salt is usually an aid to thedetersive activity of the final composition, and may even improve thehygroscopicity of the mixture somewhat, even the least hygroscopic ofthe usual builder salts cannot usually by itself eliminate the problemof caking in such compositions.

The anti-caking component of. the present detergent composition, whichtends to prevent caking due to its high melting point and/or itsresistance to deliquesce at normal or above-normal conditions ofatmospheric tempcrature and humidity is a salt selected from the classof compounds referred to as the alkyl aromatic sulfonate salts of metalsselected from the elements of groups ll and III of the periodic table,particularly the salts of magnesium, calcium, strontium, barium,aluminum, and zinc. in which one or more alkyl radicals may besubstituted on the aryl nucleus and in which the alkyl radicals maycontain from 1 to about 18 carbon atoms per alkyl group. Of these salts,the magnesium and calcium alkyl aromatic sulfonate salts areparticularly preferred because of their high order of effectiveness. Thealkyl aromatic sulfonates in which a single long chain alkyl group orseveral shorter chain alkyl groups are substituted on the aryl nucleusare preferred anti-caking components in the present composition, due tothe progressive reduction in solubility of the group II and III metalsulfonates as the chain length of the alkyl group or groups increasesand as the number of such groups substituted on the aryl nucleusincreases. For this reason it is also preferred that the aryl nucleus ofthe anti-caking component be benzenoid, rather than polycyclic, althoughcertain members of the short chain alkyl substituted naphthalenes alsoform effective anti-hygroscopic agents which may be used in the presentcomposition. The anti-caking agents herein provided, selected from thealkyl aromatic sulfonic acid salts of the metallic elements of groups IIand III of the periodic table are effective in the detergent compositionin amounts even as low as about 1% by weight of the final composition,although amounts as high as 50% of the composition may be used. Ananticaking agent content of from about 5 to about 20% by weight of thecomposition is, however, preferred. In many cases the anti-caking agentmay be a group II or group III metal salt of the same anion present inthe alkali metal detergent salt.

The anti-caking agents of the present composition selected from theaforementioned sulfonate salts are usually relatively less soluble inaqueous solutions of the detergent than the corresponding sodium salts,although they have, in general, a fair degree of solubility. It isdesirable, when a completely water-soluble detergent composition isdesired, to incorporate into the detergent composition a sequesteringagent which enhances the solubility of the anti-caking component inaqueous solution. An insoluble component in a detergent compositionintended for laundry purposes or other uses in which a clear aqueoussolution of the detergent is desirable would tend to reduce the utilityand wide acceptance of the composition for detergent purposes, and ittherefore becomes desirable to incorporate into the composition thepresent sequestering agent component in order to solubilize theanti-caking component in the detergent solution; however, where thepresence of a flocculent, insoluble precipitate does not necessarilyrender the detergent composition ineffective or undesirable for aparticular deterging operation, the sequestering agent component wouldnot be a necessary ingredient in the present composition. Suitableorganic and inorganic compounds which may be utilized in the presentcomposition as sequestering agents include two general classes ofmaterials: (1) the socalled versenes or sequestrenes and (2) the alkalimetal polyphosphate salts which in general are characterized as thealkali metal salts of phosphoric acid from which the water of hydrationhas been partially removed. Typical compounds selected from the abovetwo classes of materials include the tetra-acetate salts ofethylenediamine, the monoalkyl ethylenediamine triacetate salts,

such as the sodium salt of N-ethyl-ethylene-diarnine triacetate, theN,N-dialkyl-ethylenediamine-diacetates, sodium tetraphosphate,tetrasodium pyrop'hosphate, sodium hexametaphosphate, and sodiumtripolyphosphate. Thesequestering agent is incorporated into thedetergent compound in amounts representing stoichiometric proportions,based on the quantity of anti-caking component in the composition, inamounts sufficient to form a watersoluble complex with the anti-cakingagent when the detergent composition is added to Water preparatory tothe deterging operation. An additional quantity of sequestering agentmay be added, however, to overcome the hardness of the water in whichthe detergent is used. Although the amount of sequestering agent in thecomposition required to solubilize the anti-caking component isproportional to the amount of the latter component in the compositionand also proportional to the valence of the metallic salts selected forthe anti-caking component, the amount is generally from about 1 to about25 by weight of the composition, and preferably from about 5 to about byweight thereof. In the case of the polyphosphates, however, largerquantities, as much as 50% or even higher, may be incorporated, becauseof the excellent building qualities of such salts. For certaindetergents Which deliquesce rapidly in contact with atmospheric humidityor which have relatively low melting points, larger quantities of theanti-caking component are required to prevent the undesirable cakingtendency of the final composition and the amount of sequestering agentrequired to solubilize the anti-caking component is accordinglyproportionately increased. It is generally preferable, however, toincorporate an excess of the sequestering agent in the composition inorder to insure substantially complete solubilization of the anti-cakingcom-- ponent even in the presence of added water hardness.

In order to maintain the desired activities of the several components ofthe present detergent composition until the composition is used in adeterging operation, it is essential that the reaction between theanti-caking component and the sequestering agent be suspended until thedetergent composition is added to water preparatory to its use in adeterging operation. it therefore becomes essential to prevent the ionicexchange between the anticaking component and the sequestering agentwhile the composition is in its packaged form prior to its dissolutionin water. Thus, in compositing the components of the present compositionthe dry anti-caking component may be added to a previously driedsolution or slurry formed of a mixture of the detergent and sequesteringComponent, or, alternatively, the dry sequestering agent may beincorporated with a previously dried mixture of the detergent andanti-caking component. Since the greatest anti-hygroscopic effect isobtained by intimately mixing the anti-caking component with thedetergent component, preferably by forming an aqueous slurry of thelatter two ingredients and thereafter drying the resulting slurry to ananhydrous condition, it is generally preferred to add the drysequestering agent to a previously dried mixture of the anti-cakingcomponent and the detergent ingredient. Although aqueous slurrying ofthe detergent and anti-caking component is generally preferred to obtainthe most intimate admixture thereof and a resulting reduced tendency toundergo caking upon storage, any other means of compositing may also beemployed, as for example, by grinding the detergent and anti-cakingcomponent together in the form of a fine powder and thereafter mixing inthe sequestering component, or the separate components may be mixed indry, powdered form immediately preceding the packaging of the mixture.

In addition to the essential components of the present composition, thatis, the detergent, the anti-caking component and the sequestering agent,the composition may also contain other components common to many of theconventional detergent compositions presently on the market, such as theaforementioned builder salts, water alkalizing agents such as sodiumcarbonate, sodium silicate, trisodium phosphate, and borax;pH-controlling agents when the alkalinity of the detergent compositionis desirably reduced, such as the alkali metal salts of the lower fattyacids, including sodium acetate, sodium propionate, sodium butyrate,etc.; pigments, particularly bluings or dyes which fluoresce blue;abrasives and fillers,

such as silica, pumice, chalk, talc, Pullers earth and the like;perfumes and deodorants; germicides, such as phenol, resorcinol,mercuric chloride, phenyl mercury chloride and others; bleaching agentssuch as sodium hydrosulphite, ammonium thiosulphate, and others; soilsuspending agents, such as sodium carboxymethyl cellulose,-

, tion, thereby forming roughly spherical particles having free-flowingcharacteristics when poured from their packaging containers. inaccordance with this method, which may be well adapted to comminution ofthe present detergent composition, an aqueous suspension, slurry orsolution of the detergent and the sequestering agent or the detergentand the anti-caking component is sprayed into a hot, dry atmosphere andthe resulting droplets suspended therein until the Water has beenevaporated therefrom, forming a dry residue of solid ingredients inroughly spherical form. In carrying out this method, in which an aqueousslurry or solution is formed prior to the spray drying, it is essentialthat no combination of components'be formed which is capable of reactingin the presence of water whereby the aforementioned ionic exchangereaction between the anti-caking component and the sequestering agentcan take place While the com.- ponents are contacted in the presence ofwater. Thus, if a slurry is prepared containing the detergent and theanti caking component and the resulting slurry spray dried, thesequestering agent is added to the dried par-' ticles following thespray drying and preferably admixed therewith in powdered form.Alternatively, the anticaking component may be added in powdered form toa spray dried slurry of the detergent and the sequestering agentpreviously in aqueous suspension or solution. Other methods ofcomminution include extrusion or pelleting the dried components of thecomposition whereby the latter, generally in finely divided, powderedform are compressed into a confining space and thereafter ejected in theform of hard, regularly shaped particles. Suitable binding agents, suchas water-soluble rosin derivatives or plasticizers may be added to thepowdered components prior to the extrusion in order to form astructurally rigid particle with the added binder holding the driedparticles together. Still another method of comminution is thewell-known drum drying method in which an aqueous suspension of twocompatible components of the composition is spread as a thin film on thesurface of a rotating heated drum, the dried residue being scrapedtherefrom in the form of small platelets or chips. The drumdriedparticles may thereafter be tumbled with the remaining component of thecomposition, such as the anti.

caking component, in the dry state.

to the following examples which illustrate the process and compositionof this invention relative to specific embodiments thereof. The examplesare not intended,

however, to limit the generally broad scope of the invention ashereinabove specified.

7 EXAMPLE Aseries of detergent compositions which are normallyhygroscopic and cake rapidly when exposed to atmospheric humidity,consisting of mixtures of 60% by weight of sodium sulfate and 40% byweight of the organic detergent component was prepared and various alkylaromatic sulfonate salts of metals selected from groups II and III ofthe periodic table were admixed in the presence of water with thedetergent-sodium sulfate mixture, forming a mixture of sodium sulfate,detergent and the alkyl aromatic sulfonate salt of a group II or groupIII metal. The aqueous slurry was thereafter dried on a heated rotatingdrum from which small detergent composition chips were scraped. Thelatter were subsequently composited with a dry sequestering agent andthe detergency of the resulting compositions determined. The flaked,drum-dried product containing the anti-caking component, but not thesequestering agent was dried at 130 C. for ten hours for each testsample of detergent composition in order to a Table I.Adsrpti0n ofmoisture by detergent compositions in an atmosphere of 88% relativehumidity at 25 C.

H20 Content 2?: g' Detergent Composi- Additive, Wt. Perfi timeStabiltion cent (Hrs) ity ,}1; before Facc'ent calting tor P SDBS NaiSO433 1 SDTS NMSO4 20 1 LS NaaSO4 50 l SDBS -NazSO4 102 3. l SDBS -NazSO4106 3. 2 SDTS NazSO4 C 52 2. 6 SDTS -N32S04 42 2. 1

SDTS N82S04 58 2. 9

Ls NB.ZSO4 o 180 3. o SDTS NazSO4 36 1. 8 SDTS N!MSO4 92. 5 2. 8

1 Sodium dodecylbenzene sulfonate.

Sodium dodecyltoluene sulfonate.

3 Laurylsultate (sodium salt).

4 Calcium dodecylbenzene sulfonate.

5 Magnesium dodecylbenzene sulfonate. 6 Aluminum dodecylbenzenesulfonate. 1 Calcium toluene sulfonate.

5 Calcium dodecyltoluene sulfonate.

' Stoarge stability factor is a numerical value representing therelative I merits of the additive anti-caking component in preventingeaking. Its value is determined by dividing the number of hours for thecomposition containing the additive to cake by the number of hours forthe particular composition sans the anti-coking additive. For a mixtureof the detergent and sodium sulfate, the factor is necessarily 1.

The above results indicate that incorporation of an alkyl aromaticsulfonate salt of a metal selected from groups II and III of theperiodic table into a normally hygroscopic detergent compositioncontaining a detergent and a builder salt increases the time requiredbefore caking from to 50 hours to 42 to 180 hours and that the additionof a sequestering agent to the composition does not substantially alterthe time before caking occurs. The above compositions into which asequestering agent, such as sodium tripolyphosphate was incorporatedwere readily dissolved in water without the formation of an insolublehaze in the resulting solution. The detergency of the resulting mixtureswas in each case substantially equal to or better than the compositionsfrom which the anticaking component and the sequestering agents wereabsent.

We claim as our invention:

1. A comminuted detergent composition comprising a free-flowingwater-soluble mixture of finely divided solid particles of: (1) ananionic detergent selected from the group consisting of the alkalimetal, ammonium, alkyl ammonium and hydroxy-alkyl ammonium salts of analkyl aromatic sulfonic acid containing an alkyl group of from about 9to about 18 carbon atoms; (2) an alkyl benzene sulfonate salt of a metalselected from the group consisting of magnesium, calcium, strontium,barium, aluminum and zinc, the last-mentioned salt having an alkyl groupof from 1 to about 18 carbon atoms and being in sufiicient amount toprevent caking of said detergent, and (3) a suificient amount of asequestering agent to enhance the solubility of the last-mentionedsulfonate salt.

2. The composition of claim 1 further characterized in that said alkylbenzene sulfonate is an alkaline earth metal sulfonate salt.

3. The composition of claim 2 further characterized in that saidalkaline earth metal salt is a calcium alkyl benzene sulfonate salt.

4. The composition of claim 2 further characterized in that saidalkaline earth metal salt is a magnesium alkyl benzene sulfonate salt.

5. The composition of claim 1 further characterized in that the metal ofsaid alkyl benzene sulfonate is aluminum.

6. The composition of claim 1 further characterized in that anionicdetergent is a sodium alkylbenzene sulfonate.

7. A comminuted detergent composition comprising a free-flowingwater-soluble mixture of finely divided solid particles of a sodiumalkylbenzene sulfonate detergent having an alkyl group of from about 9to about 18 carbon atoms, an alkaline earth metal sulfonate salt of analkyl benzene sulfonic acid, the last-mentioned salt having an alkylgroup of from 1 to about 18 carbon atoms and being in SUlfiClBIlt amountto prevent caking of said detergent, and a sufficient amount of asequestering agent to enhance the solubility of said alkaline earthmetal sulfonate salt.

8. The composition of claim 1 further characterized in that said anionicdetergent comprises a sodium alkyltoluene sulfonate.

9. The composition of claim 1 further characterized in that saidsequestering agent is an alkali metal, molecularly dehydrated complexphosphate salt.

10. The composition of claim 9 further characterized in that saidcomplex salt is sodium tripolyphosphate.

11. The composition of claim 9 further characterized in that saidcomplex phosphate salt is sodium hexametaphosphate.

12. The composition of claim 9 further characterized in that saidcomplex phosphate salt is tetrasodiumpyrophosphate.

13. The composition of claim 1 containing from about 5 to about 20% byweight of said alkyl benzene sulfonate salt of a metal.

14. The composition of claim 1 containing from 1 to about 25% by weightof said sequestering agent.

15. The composition of claim 1 further characterized in that saidanionic detergent comprises sodium dodecylbenzene sulfonate.

16. The composition of claim 1 further characterized in that saidanionic detergent comprises sodium dodecyltoluene sulfonate.

17. The composition of claim 7 further characterized in that thefirst-mentioned sulfonate is sodium dodecyltoluene sulfonate.

18. The composition of claim 7 further characterized in that thefirst-mentioned sulfonate is sodium dodecylbenzene sulfonate.

References Cited in the file of this patent UNITED STATES PATENTS1,956,515 Hall Apr. 24, 1934 2,283,199 Flett May 19, 1942 2,486,922Strain Nov. 1, 1949 2,542,385 Ayo Feb. 20, 1951 2,617,772 Keenan Nov.11, 1952

1. A COMMINUTED DETERGENT COMPOSITION COMPRISING A FREE-FLOWINGWATER-SOLUBLE MIXTURE OF FINELY DIVIDED SOLID PARTICLES OF: (1) ANANIONIC DETERGENT SELECTED FROM THE GROUP CONSISTING OF THE ALKALIMETAL, AMMONIUM, ALKYL AMMONIUM AND HYDROXY-ALKYL AMMONIUM SALTS OF ANALKYL AROMATIC SULFONIC ACID CONTAINING AN ALKYL GROUP OF FROM ABOUT 9TO 18 CARBON ATOMS; (2) AN ALKYL BENZENE SULFONATE SALT OF A METALSELECTED FROM THE GROUP CONSISTING OF MAGNESIUM, CALCIUM, STRONTIUM,BARIUM, ALUMINUM AND ZINC, THE LAST-MENTIONED SALT HAVING AN ALKYL GROUPOF FROM 1 TO ABOUT 18 CARBON ATOMS AND BEING IN SUFFICIENT AMOUNT TOPREVENT CAKING OF SAID DETERGENT,AND (3) A SUFFICIENT AMOUNT OF ASEQUESTERING AGENT TO ENHANCE THE SOLUBILITY OF THE LAST-MENTIONEDSULFONATE SALT.
 9. THE COMPPOSITION OF CLAIM 1 FURTHER CHARACTERIZED INTHAT SAID SEQUESTING AGENT IS AN ALKYL METAL, MOLECULARLY DEHYDRATEDCOMPLEX PHOSPHATE SALT.